Fluorinated ether compound, fluorinated ether composition and coating liquid, and substrate having surface-treated layer and method for its production

ABSTRACT

A fluorinated ether compound which has a poly(oxyperfluoroalkylene) chain (αβ) having a structure of block (α)-block (β) or a structure of block (β)-block (α)-block (β), formed by linking a block (α) comprising at least three C 1-3  oxyperfluoroalkylene units of at least one type and a block (β) having C 4-15  oxyperfluoroalkylene units of at least one type, wherein the proportion of the C 4-15  oxyperfluoroalkylene units is at least 30 mol % among all oxyperfluoroalkylene units constituting the block (β), and which has a hydrolysable silyl group on at least one terminal of the poly(oxyperfluoroalkylene) chain (αβ) via a linking group. Also, a fluorinated ether composition and a coating liquid, whereby it is possible to form a surface-treated layer which has high initial water/oil repellency and which is excellent in abrasion resistance and finger print stain removability, and a substrate having a surface-treated layer and a method for its production.

TECHNICAL FIELD

The present invention relates to a fluorinated ether compound, afluorinated ether composition or a coating liquid containing such afluorinated ether compound, which is useful for surface treatment toimpart water/oil repellency to a substrate surface. The presentinvention relates also to a method for producing a substrate having asurface-treated layer by using such a compound, a fluorinated ethercomposition or a coating liquid, and a substrate having asurface-treated layer produced by such a method.

BACKGROUND ART

A fluorinated compound is useful as a surface treating agent since ithas high lubricity, water/oil repellency, etc. By imparting water/oilrepellency to a substrate surface by such a surface treating agent,stains on the substrate surface will easily be wiped off, and stainremovability will be improved. Among such fluorinated compounds, afluorinated ether compound having a poly(oxyperfluoroalkylene) chain inwhich an ether bond (—O—) is present in the middle of a perfluoroalkylchain is particularly excellent in the fat and oil stain removability.

A surface treating agent containing such a fluorinated ether compound isuseful in applications wherein it is desired to maintain a performance(abrasion resistance) whereby the water/oil repellency is less likely tobe reduced even if repeatedly rubbed by fingers, and a performance(fingerprint stain removability) whereby fingerprints deposited on asurface can easily be removed by wiping, for a long period of time, e.g.as a surface treating agent for a member constituting a surface to betouched by a finger, of a touch panel.

As such fluorinated ether compounds, specifically, fluorinated ethercompounds of the following (1) to (4) are known.

(1) A fluorinated ether compound having a structure wherein (CF₂O) unitsand (CF₂CF₂O) units are randomly linked, and having a hydrolysable silylgroup at a terminal (Patent Document 1)

(2) A fluorinated ether compound having a structure wherein at least twotypes of units selected from the group consisting of (CF₂O) units,(CF₂CF₂O) units, (CF₂CF₂CF₂O) units and (CF(CF₃)CF₂O) units are randomlylinked, and having a hydrolysable silyl group at a terminal (PatentDocuments 2 to 5)

(3) A fluorinated ether compound having a structure wherein only(CF₂CF₂CF₂O) units or (CF(CF₃)CF₂O) units are linked, and having ahydrolysable silyl group at a terminal (Patent Documents 6 and 7)

(4) A fluorinated ether compound having a structure wherein only(CF₂CF₂CF₂CF₂O) units are linked, and having a hydrolysable silyl groupat a terminal (Patent Document 8)

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: Japanese Patent No. 4,138,936-   Patent Document 2: JP-A-2008-534696-   Patent Document 3: WO2011/060047-   Patent Document 4: WO2011/059430-   Patent Document 5: Japanese Patent No. 2,874,715-   Patent Document 6: JP-A-2000-144097-   Patent Document 7: JP-A-11-029585-   Patent Document 8: JP-A-2002-506887

DISCLOSURE OF INVENTION Technical Problem

According to findings by the present inventor, the fluorinated ethercompound of (1) is relatively good in abrasion resistance andfingerprint stain removability, but is sometimes inadequate in water/oilrepellency at the initial stage before repeated abrasion.

The fluorinated ether compound of (2) is improved in water/oilrepellency at the initial stage as compared with the fluorinated ethercompound of (1), but is still sometimes inadequate, and in abrasionresistance and fingerprint stain removability, it is inferior to thefluorinated ether compound of (1).

The fluorinated ether compounds of (3) and (4) are excellent inwater/oil repellency at the initial stage, but are inadequate inabrasion resistance and fingerprint stain removability.

It is an object of the present invention to provide a fluorinated ethercompound, a fluorinated ether composition and a coating liquid,containing the fluorinated ether compound, whereby it is possible toform a surface-treated layer having high initial water/oil repellencyand being excellent in abrasion resistance and fingerprint stainremovability.

It is also an object of the present invention to provide a substratehaving a surface-treated layer having high initial water/oil repellencyand being excellent in abrasion resistance and fingerprint stainremovability, and a method for its production.

Solution to Problem

The present invention provides a fluorinated ether compound, afluorinated ether composition and a coating liquid, and a substratehaving a surface-treated layer and a method for its production, with thefollowing constructions [1] to [15].

[1] A fluorinated ether compound which has a poly(oxyperfluoroalkylene)chain (αβ) having a structure of block (α)-block (β) or a structure ofblock (β)-block (α)-block (β), formed by linking a block (α) comprisingat least three C₁₋₃ oxyperfluoroalkylene units of at least one type anda block (β) having C₄₋₁₅ oxyperfluoroalkylene units of at least onetype, wherein the proportion of the C₄₋₁₅ oxyperfluoroalkylene units isat least 30 mol % among all oxyperfluoroalkylene units constituting theblock (β), and which has a hydrolysable silyl group on at least oneterminal of the poly(oxyperfluoroalkylene) chain (αβ) via a linkinggroup.[2] The fluorinated ether compound according to [1], wherein a C₁₋₆perfluoroalkyl group or a C₂₋₆ perfluoroalkyl group having an ethericoxygen atom is bonded via an oxygen atom to the carbon atom at one endof the poly(oxyperfluoroalkylene) chain (αβ), and the hydrolysable silylgroup is bonded via the linking group to the oxygen atom at the otherend of the poly(oxyperfluoroalkylene) chain (αβ).[3] The fluorinated ether compound according to [2], wherein thepoly(oxyperfluoroalkylene) chain (αβ) is a poly(oxyperfluoroalkylene)chain having a structure of block (α)-block (β), and the hydrolysablesilyl group is bonded via the linking group to the oxygen atom of theblock (β).[4] The fluorinated ether compound according to [1], wherein thehydrolysable silyl group is bonded via the linking group to each end ofthe poly(oxyperfluoroalkylene) chain (αβ).[5] The fluorinated ether compound according to any one of [1] to [4],which has a number average molecular weight of from 2,000 to 10,000.[6] The fluorinated ether compound according to any one of [1] to [5],wherein the block (β) has (CF₂CF₂CF₂CF₂O) units.[7] A fluorinated ether composition containing at least 95 mass % of thefluorinated ether compound as defined in any one of [1] to [6].[8] A coating liquid comprising the fluorinated ether compound asdefined in any one of [1] to [6], and a medium.[9] The coating liquid according to [8], wherein the medium contains atleast one organic solvent selected from the group consisting of afluorinated alkane, a fluorinated aromatic compound, a fluoroalkylether, and a non-fluorinated organic solvent being a compound composedsolely of hydrogen atoms, carbon atoms and oxygen atoms.[10] A method for producing a substrate having a surface-treated layer,which comprises a step of applying the fluorinated ether compound asdefined in any one of [1] to [6] or the fluorinated ether composition asdefined in [7] to the surface of a substrate by vacuum deposition.[11] A method for producing a substrate having a surface-treated layer,which comprises a step of applying the coating liquid as defined in [8]or [9] to the surface of a substrate, followed by dying.[12] The method for producing a substrate having a surface-treated layeraccording to [11], wherein the method of applying the coating liquid tothe surface of the substrate is a spin coating method, a wipe coatingmethod, a spray coating method, a squeegee coating method, a dip coatingmethod, a die coating method, an ink jet method, a flow coating method,a roll coating method, a casting method, a Langmuir-Blodgett method or agravure coating method.[13] The method for producing a substrate having a surface-treated layeraccording to any one of [10] to [12], wherein the material for thesubstrate is a metal, a resin, glass, a ceramic or a composite materialthereof.[14] A substrate having a surface-treated layer, obtained by treatmentwith the fluorinated ether composition as defined in [7].[15] A touch panel having, on its input screen, the substrate having asurface-treated layer, obtained by treatment with the fluorinated ethercomposition as defined in [7].

Advantageous Effects of Invention

By the fluorinated ether compound, the fluorinated ether composition andthe coating liquid, containing the fluorinated ether compound, of thepresent invention, it is possible to form a surface-treated layer havinghigh initial water/oil repellency and being excellent in abrasionresistance and fingerprint stain removability.

The substrate having a surface-treated layer of the present inventionhas a surface-treated layer having high initial water/oil repellency andbeing excellent in abrasion resistance and fingerprint stainremovability.

According to the method for producing a substrate having asurface-treated layer of the present invention, it is possible toproduce a substrate having a surface-treated layer having high initialwater/oil repellency and being excellent in abrasion resistance andfingerprint stain removability.

DESCRIPTION OF EMBODIMENTS

In this specification, a compound represented by the formula (1) will bereferred to as a compound (1). Compounds and precursors represented byother formulae will be referred to in the same manner.

In the present invention, the main chain is a linear molecular chainwhereby all molecular chains other than the main chain would be deemedto be side chains.

In the present invention, a hydrolysable silyl group is a group capableof forming a silanol group (Si—OH) when hydrolyzed. For example,—SiL_(m)R_(3-m) in the formula (1) may be mentioned.

In the present invention, an etheric oxygen atom is an oxygen atom toform an ether bond (—O—) between carbon-carbon atoms.

In the present invention, a linking group is a group to link apoly(oxyperfluoroalkylne) chain (αβ) and a hydrolysable silyl group, andis, for example, a group having —SiL_(m)R_(3-m) excluded from B in theformula (1), and such a group itself may have other oxyperfluoroalkylenegroup not belonging to the above poly(oxyperfluoroalkylne) chain (αβ).Further, hereinafter, a poly(oxyperfluoroalkylne) chain (αβ) will bereferred to also as a “chain (αβ)”.

In the present invention, the number average molecular weight of afluorinated ether compound is calculated by the following method using aNMR analysis.

It is calculated by obtaining the number (average value) ofoxyperfluoroalkylne units by using a terminal group as a standard, bymeans of ¹H-NMR (solvent: deuterated acetone, internal standard: TMS)and ¹⁹F-NMR (solvent: deuterated acetone, internal standard: CFCl₃). Theterminal group is, for example, A or B in the formula (1).

In the present invention, a chemical formula of an oxyperfluoroalkyleneunit shall be presented so that its oxygen atom be on the right-handside of the perfluoroalkylene group. Each of a block (α) and a block (β)is a bivalent group formed by repetition of an oxyperfluoroalkyleneunit, wherein one of the two terminals is a connecting bond bonded to acarbon atom and the other is a connecting bond of an oxygen atom. Achemical formula of such a block shall be presented so that the terminaloxygen atom be on the right-hand side. A poly(oxyperfluoroalkylene)chain (αβ) formed by linkage of the above blocks, is also a linearbivalent group, wherein one of the two terminals is a connecting bondbonded to a carbon atom (the carbon atom having this connecting bondwill be referred to as a terminal carbon atom) and the other is aconnecting bond of an oxygen atom (the oxygen atom having thisconnecting bond will be referred to as a terminal oxygen atom). Achemical formula of a poly(oxyperfluoroalkylene) chain (αβ) shall alsobe presented so that the terminal oxygen atom be on the right-hand side.

In the present invention, a surface-treated layer is a layer formed onthe surface of a substrate, by surface treatment of the substrate withthe fluorinated ether compound, the fluorinated ether composition or thecoating liquid of the present invention.

[Fluorinated Ether Compound]

The fluorinated ether compound of the present invention (hereinafterreferred to as the present compound) is a compound having a structure ofblock (α)-block (β), or a compound having a structure of block (β)-block(α)-block (β). Hereinafter, the former will be referred to as the firstembodiment of the present compound, and the latter will be referred toas the second embodiment of the present compound.

The present compound has a hydrolysable silyl group on at least oneterminal of the chain (αβ) via a linking group. The chain (αβ) ispresent preferably in the main chain. The number of hydrolysable silylgroups bonded to a linking group may be two or more, and is preferablyfrom 1 to 3, more preferably 1 or 2, particularly preferably 1. Thelinking group is a polyvalent group having one connecting bond bonded tothe chain (αβ) side and at least one connecting bond bonded to a siliconatom in the hydrolysable silyl group, and in a case where the number ofhydrolysable silyl groups bonded to the linking group is 1, the linkinggroup is a bivalent group. The connecting bond of the linking groupbonded to the chain (αβ) side, is a connecting bond of a carbon atomwhen the linking group is bonded to a terminal oxygen atom of the chain(αβ) and is a connecting bond of an oxygen atom when the linking groupis bonded to a terminal carbon atom of the chain (αβ). The connectingbond of the linking group bonded to a silicon atom of a hydrolysablesilyl group is a connecting bond of a carbon atom.

In a case where the present compound does not have a hydrolysable silylgroup via a linking group at one terminal of the chain (αβ), it has amonovalent organic group at that terminal. In a case where a monovalentorganic group is bonded to a terminal carbon atom of the chain (αβ), itis bonded via an oxygen atom. In a case where a monovalent organic groupis bonded to a terminal oxygen atom of the chain (αβ), the monovalentorganic group is preferably an organic group wherein the terminal is acarbon atom. As such an organic group, a perfluoroalkyl group or aperfluoroalkyl group having an etheric oxygen atom is preferred.

First Embodiment

The first embodiment of the present compound of the present invention isa compound which has a poly(oxyperfluoroalkylene) chain (αβ) having astructure of block (α)-block (β), formed by linking a block (α)comprising at least three C₁₋₃ oxyperfluoroalkylene units of at leastone type and a block (β) having C₄₋₁₅ oxyperfluoroalkylene units of atleast one type, wherein the proportion of the C₄₋₁₅ oxyperfluoroalkyleneunits is at least 30 mol % among all oxyperfluoroalkylene unitsconstituting the block (β), and which has a hydrolysable silyl group onat least one terminal of the poly(oxyperfluoroalkylene) chain (αβ) via alinking group. The chain (αβ) is present preferably in the main chain.

The present compound may have other oxyperfluoroalkylene groups notbelonging to the chain (αβ).

The present compound may have a hydrolysable silyl group via a linkinggroup at one terminal of the chain (αβ), or may have a hydrolysablesilyl group via a linking group at each terminal of the chain (αβ). Witha view to sufficiently imparting abrasion resistance to thesurface-treated layer, it preferably has a hydrolysable silyl group onlyat one terminal of the chain (αβ).

The present compound may be a single compound or a mixture of two ormore types different in the chain (αβ), the terminal group, the linkinggroup, etc.

The block (α) is a block comprising at least three C₁₋₃oxyperfluoroalkylene units. Such a block may be constituted solely byoxyperfluoroalkylene units of one type having the same number of carbonatoms, or may be constituted by oxyperfluoroalkylene units of two orthree types different in the number of carbon atoms.

The block (β) is a block having C₄₋₁₅ oxyperfluoroalkylene units,wherein the proportion of the C₄₋₁₅ oxyperfluoroalkylene units is atleast 30 mol % among all oxyperfluoroalkylene units constituting theblock (β). Such a block may be constituted solely byoxyperfluoroalkylene units of one type having the same number of carbonatoms, or may be constituted by oxyperfluoroalkylene units of at leasttwo types different in the number of carbon atoms. Further, such a blockmay have C₁₋₃ oxyperfluoroalkylene units.

The block (β) is preferably one having (CF₂CF₂CF₂CF₂O) units, since itis thereby possible to impart sufficiently high initial water/oilrepellency to the surface-treated layer.

The present compound has the block (α) whereby the abrasion resistanceand fingerprint stain removability of the surface-treated layer will beexcellent, and it has the block (β) whereby the initial water/oilrepellency of the surface-treated layer will be excellent.

The present compound is preferably a compound wherein to a carbon atomat one end of the chain (αβ), a C₁₋₆ perfluoroalkyl group, or a C₂₋₆perfluoroalkyl group having an etheric oxygen atom, is bonded via anoxygen atom, and to an oxygen atom at the other end of the chain (αβ), ahydrolysable silyl group is bonded via a linking group. By such aconstruction, the initial water/oil repellency, abrasion resistance andfingerprint stain removability at the surface-treated layer will befurther improved.

The first embodiment of the present compound is preferably a compoundwherein in the chain (αβ), a hydrolysable silyl group is bonded to anoxygen atom of a block (αβ) via a linking group. In other words, acompound wherein a perfluoroalkyl group is bonded to a carbon atom of ablock (α) via an oxygen atom, is preferred. By such a construction, theabrasion resistance and fingerprint stain removability at thesurface-treated layer will be further improved. The reason is consideredto be such that a block (α) to impart the abrasion resistance andfingerprint stain removability to the surface-treated layer may bepresent on the side close to the surface of the surface-treated layer.

When the present compound has a perfluoroalkyl group at its terminal,the initial water/oil repellency at the surface-treated layer will befurther improved.

Second Embodiment

The second embodiment of the present compound of the present inventionis a compound which has a poly(oxyperfluoroalkylene) chain (αβ) having astructure of block (β)-block (α)-block (β), formed by linking a block(α) comprising at least three C₁₋₃ oxyperfluoroalkylene units of atleast one type and a block (β) having C₄₋₁₅ oxyperfluoroalkylene unitsof at least one type, wherein the proportion of the C₄₋₁₅oxyperfluoroalkylene units is at least 30 mol % among alloxyperfluoroalkylene units constituting the block (β), and which has ahydrolysable silyl group on at least one terminal of thepoly(oxyperfluoroalkylene) chain (αβ) via a linking group.

The present compound may have other oxyperfluoroalkylene groups notbelonging to the chain (αβ).

The present compound may have a hydrolysable silyl group via a linkinggroup at one terminal of the chain (αβ) or may have a hydrolysable silylgroup via a linking group at each terminal of the chain (αβ). With aview to sufficiently imparting abrasion resistance to thesurface-treated layer, it preferably has a hydrolysable silyl group viaa linking group at each terminal of the chain (αβ).

The present compound may be a single compound or a mixture of two ormore types different in the chain (αβ), the terminal group, the linkinggroup, etc.

The block (α) and the block (β) are the same as in the first embodiment.

The second embodiment of the present compound is preferably a compoundwherein at each end of the chain (αβ), a hydrolysable silyl group isbonded via a linking group. When a hydrolysable silyl group is bondedvia a linking group at each end of the chain (αβ), a block (β) will beon the side close to the substrate, and as a result, a block (α) toimpart the abrasion resistance and fingerprint stain removability to thesurface-treated layer may be present on the side close to the surface ofthe surface-treated layer. By such a construction, the initial water/oilrepellency, abrasion resistance and fingerprint stain removability atthe surface-treated layer will be further improved.

Common to First and Second Embodiments

The number average molecular weight of the present compound ispreferably from 2,000 to 10,000. When the number average molecularweight is within such a range, the present compound is excellent in theabrasion resistance. The number average molecular weight of the presentcompound is more preferably from 2,100 to 9,000, particularly preferablyfrom 2,400 to 8,000.

Usually, it is considered that with a fluorinated ether compound, thechemical bond to a substrate becomes strong as the number averagemolecular weight decreases. The reason is considered to be such that thenumber of hydrolysable silyl groups increases per unit molecular weight.However, the present inventors have confirmed that if the number averagemolecular weight is less than the lower limit value within the aboverange, the abrasion resistance is likely to decrease. Further, if thenumber average molecular weight exceeds the upper limit value within theabove range, the abrasion resistance decreases. The reason is consideredto be such that the influence due to a decrease in the number ofhydrolysable silyl groups present per unit molecular weight tends to belarge.

The present compound has a poly(oxyperfluoroalkylene) chain, whereby thecontent of fluorine atoms is large. Further, as mentioned above, it hasa poly(oxyperfluoroalkylene) chain (αβ) wherein a block (α) to impartabrasion resistance and fingerprint stain removability to thesurface-treated layer and a block (β) to impart high initial water/oilrepellency to the surface-treated layer are linked. Therefore, thepresent compound is capable of forming a surface-treated layer havinghigh initial water/oil repellency and being excellent in abrasionresistance and fingerprint stain removability.

In surface treatment with the present compound, the fluorinated ethercomposition or the coating liquid, as described later, silanol groups(Si—OH) will be formed by a hydrolytic reaction of hydrolysable silylgroups (—SiL_(m)R_(3-m)) in the present compound, and such silanolgroups will be intermolecularly reacted to form Si—O—Si bonds, or suchsilanol groups will undergo a dehydration-condensation reaction withhydroxy groups (substrate-OH) at the surface of a substrate to formchemical bonds (substrate-O—Si). That is, the surface-treated layer inthe present invention contains the present compound in such a state thatsome or all of hydrolysable silyl groups in the present compound arehydrolyzed.

Compound (1)

A preferred embodiment of the first embodiment of the present compoundis specifically represented by the following formula (1).A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—B  (1)

Here, the symbols in the formula (1) are as follows.

x1: an integer of at least 3.

x2 to x3: x2 is an integer of 0 or at least 1, x3 is an integer of atleast 1, and x3/(x2+x3)×100 is at least 30.

R^(f1): C₁₋₃ perfluoroalkylene group of at least one type

R^(f2): C₁₋₃ perfluoroalkylene group of at least one type

R^(f3): C₄₋₁₅ perfluoroalkylene group of at least one type

A: a C₁₋₆ perfluoroalkyl group, a C₂₋₆ perfluoroalkyl group having anetheric oxygen atom, or B

B: a group represented by one of the following formulae (2-1) to (2-4)—R^(f4)CX₂O(CH₂)₃—SiL_(m)R_(3-m)  (2-1)—R^(f4)CX₂OCH₂CH(CH₃)—SiL_(m)R_(3-m)  (2-2)—R^(f4)C(═O)NHC_(k)H_(2k)—SiL_(m)R_(3-m)  (2-3)—R^(f4)(CH₂)₂—SiL_(m)R_(3-m)  (2-4)

Here, the symbols in the formulae (2-1) to (2-4) are as follows.

R^(f4): a C₁₋₂₀ perfluoroalkylene group which may have an etheric oxygenatom

X: a hydrogen atom or a fluorine atom

L: a hydrolysable group

R: a hydrogen atom or a monovalent hydrocarbon group

k: an integer of at least 1

m: an integer of from 1 to 3

<Block (α)>

In the formula (1), the block (α) is the portion represented by{(R^(f1)O_(x1)}.

x1 is an integer of at least 3. With a view to imparting sufficientabrasion resistance and fingerprint stain removability to thesurface-treated layer, it is preferably an integer of at least 4,particularly preferably an integer of at least 5. If the number averagemolecular weight of the compound (1) is too large, the number ofhydrolysable silyl groups present per unit molecular weight decreasesand the abrasion resistance decreases, and therefore, the upper limit ofx1 is preferably 20, particularly preferably 15.

R^(f1) is a C₁₋₃ perfluoroalkylene group of at least one type. From theviewpoint of the thermal or chemical stability of the compound (1),R^(f1) is preferably a C₂₋₃ perfluoroalkylene group of at least onetype, and with a view to imparting sufficient abrasion resistance andfingerprint stain removability to the surface-treated layer, it isparticularly preferably a C₂ perfluoroalkylene group. In a case wherethe number of carbon atoms is 2 or 3, R^(f1) may be linear or branched.With a view to imparting abrasion resistance and fingerprint stainremovability to the surface-treated layer, it is preferably linear i.e.CF₂CF₂ or CF₂CF₂CF₂.

In a case where in a block (α), two or three types of (R^(f1)O) unitsdifferent in the number of carbon atoms are present, the bonding orderof the respective (R^(f1)O) units is not limited.

<Block (β)>

In the formula (1), the block (β) is the portion represented by{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}.

x2 is an integer of 0 or at least 1. With a view to imparting sufficientinitial liquid repellency to the surface-treated layer, it is preferablyan integer of from 0 to 10, and from the viewpoint of efficiency forindustrial production of the compound (1), it is preferably the samenumber as x3.

x3 is an integer of at least 1. With a view to imparting sufficientinitial liquid repellency to the surface-treated layer, it is preferablyan integer of at least 3, particularly preferably at least 5. If thenumber average molecular weight of the compound (1) is too large, thenumber of hydrolysable silyl groups present per unit molecular weightdecreases and the abrasion resistance decreases, and therefore, theupper limit of x3 is preferably 45, particularly preferably 30.

x3/(x2+x3)×100 is at least 30, preferably at least 50, with a view toimparting sufficient initial liquid repellency to the surface-treatedlayer. That is, the proportion of (R^(f3)O) units in a block (β) ispreferably at least 50 mol % among all oxyperfluoroalkylene groups.

R^(f2) is a C₁₋₃ perfluoroalkylene group of at least one type. From theviewpoint of the thermal or chemical stability of the compound (1),R^(f2) is preferably a C₂₋₃ perfluoroalkylene group of at least onetype, and from the viewpoint of efficiency for industrial production ofthe compound (1), it is particularly preferably a C₂ perfluoroalkylenegroup. In a case where the number of carbon atoms is 2 or 3, R^(f2) maybe linear or branched. With a view to imparting initial water/oilrepellency to the surface-treated layer, it is preferably linear i.e.CF₂CF₂ or CF₂CF₂CF₂.

R^(f3) is a C₄₋₁₅ perfluoroalkylene group of at least one type. With aview to imparting initial water/oil repellency to the surface-treatedlayer, it is preferably a C₄₋₆ perfluoroalkylene group of at least onetype, particularly preferably a C₄ perfluoroalkylene group. R^(f3) maybe linear or branched. With a view to imparting initial water/oilrepellency to the surface-treated layer, it is preferably linear i.e.CF₂CF₂CF₂CF₂, CF₂CF₂CF₂CF₂CF₂ or CF₂CF₂CF₂CF₂CF₂CF₂.

In a block (β), the bonding order of (R^(f2)O) units and (R^(f3)O) unitsis not limited. Here, from the viewpoint of efficiency for industrialproduction of the compound (1) and with a view to imparting initialwater/oil repellency to the surface-treated layer, it is preferred thatone type of (R^(f2)O) unit and one type of (R^(f3)O) unit arealternately arranged, and it is particularly preferred that a (CF₂CF₂O)unit and a (CF₂CF₂CF₂CF₂O) unit are alternately arranged.

<Poly(Oxyperfluoroalkylene) Chain (αβ)>

In the formula (1), the chain (αβ) is the portion represented by[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}].

In the chain (αβ), the bonding order of blocks (α) and (β) is notlimited.

It is preferred that A-O is bonded to a carbon atom of a block (α) and Bis bonded to an oxygen atom of a block (β), since it is thereby possibleto further efficiently obtain both the characteristics due to the block(α) and the characteristics due to the block (β).

As the chain (αβ), the following are preferred from the viewpoint ofefficiency in the industrial production of the compound (1) and with aview to sufficiently imparting initial water/oil repellency, abrasionresistance and fingerprint stain removability to the surface-treatedlayer.

[{(CF₂CF₂O)_(x11))}{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]

[{(CF₂O)_(x12)(CF₂CF₂O)_(x13))}{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]

[{(CF₂CF₂CF₂O)_(x14))}{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x23)}]

Here, x11 is an integer of from 5 to 13, x12 is an integer of from 1 to20, x13 is an integer of from 1 to 10, x14 is an integer of from 3 to10, x21 is an integer of from 5 to 20, x22 is an integer of from 5 to20, and x23 is an integer of from 5 to 20.

<Group A>

A is a C₁₋₆ perfluoroalkyl group, a C₂₋₆ perfluoroalkyl group having anetheric oxygen atom, or B. From the viewpoint of abrasion resistance, aC₁₋₆ perfluoroalkyl group, or a C₂₋₆ perfluoroalkyl group having anetheric oxygen atom, is preferred. The perfluoroalkyl group may belinear or branched.

Here, according to the expression of a chemical formula in the presentinvention, the left-hand side of a chain (αβ) is a connecting bond of acarbon atom, and therefore, in a case where A is placed on the left-handside of the chemical formula as shown in the above formula (1), A isexpressed as bonded to the chain (αβ) via an oxygen atom. On the otherhand, in a case where A is placed on the right-hand side of the chemicalformula, i.e. in the case of an expression wherein A is bonded to aterminal oxygen atom of the chain (αβ), A is expressed as directlybonded to the terminal oxygen atom of the chain (αβ) without via anoxygen atom.

The following may be mentioned as specific examples of A.

As a C₁₋₆ perfluoroalkyl group,

CF₃—,

CF₃CF₂—,

CF₃(CF₂)₂—,

CF₃(CF₂)₃—,

CF₃(CF₂)₄—,

CF₃(CF₂)₅—,

CF₃CF(CF₃)—, etc.

As a C₂₋₆ perfluoroalkyl group having an etheric oxygen atom,

CF₃OCF₂CF₂—,

CF₃O(CF₂—,

CF₃O(CF₂)₄—,

CF₃O(CF₂)₅—,

CF₃OCF₂CF₂OCF₂CF₂—,

CF₃CF₂OCF₂CF₂—,

CF₃CF₂O(CF₂)₃—,

CF₃CF₂O(CF₂)₄—,

CF₃CF₂OCF₂CF₂OCF₂CF₂—,

CF₃(CF₂)₂OCF₂CF₂—,

CF₃(CF₂)₂O(CF₂)₃—,

CF₃(CF₂)₂OCF(CF₃)CF₂—,

CF₃CF(CF₃)OCF₂CF₂—,

CF₃CF(CF₃)O(CF₂)₃—,

CF₃CF(CF₃)OCF(CF₃)CF₂—,

CF₃(CF₂)₃OCF₂CF₂—, etc.

As A, the following are preferred with a view to sufficiently impartinginitial water/oil repellency, abrasion resistance and fingerprint stainremovability to the surface-treated layer.

CF₃—,

CF₃CF₂—,

CF₃(CF₂)₂—,

CF₃OCF₂CF₂—,

CF₃OCF₂CF₂OCF₂CF₂—,

CF₃CF₂OCF₂CF₂—,

CF₃CF₂O(CF₂)₃—,

CF₃CF₂O(CF₂)₄—,

CF₃CF₂OCF₂CF₂OCF₂CF₂—,

<Group B>

The compound (1) has B at one end or both ends of the chain (αβ). Whentwo B are present in one molecule, they may be the same or different.Here, as mentioned above, according to the expression of a chemicalformula in the present invention, in a case where B is placed on theleft-hand side of the chemical formula, B is expressed as bonded to theterminal carbon atom of the chain (αβ) via an oxygen atom.

B is a group represented by one of the formulae (2-1) to (2-4), and thecompound (1) has a hydrolysable silyl group represented by—SiL_(m)R_(3-m) at its terminal. From the viewpoint of handlingefficiency in the industrial production, a group represented by theformula (2-3) is particularly preferred.

Hereinafter, a compound (1) wherein B is a group represented by theformula (2-1), will be referred to as a compound (1-1), a compound (1)wherein B is a group represented by the formula (2-2), will be referredto as a compound (1-2), a compound (I) wherein B is a group representedby the formula (2-3), will be referred to as a compound (1-3), and acompound (1) wherein B is a group represented by the formula (2-4), willbe referred to as a compound (1-4).A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)CX₂O—(CH₂)₃—SiL_(m)R_(3-m)  (1-1)A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)CX₂OCH₂CH(CH₃)—SiL_(m)R_(3-m)  (1-2)A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)C(═O)NHC_(k)H_(2k)—SiL_(m)R_(3-m)  (1-3)A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)(CH₂)₂—SiL_(m)R_(3-m)  (1-4)

R^(f4) is a C₁₋₂₀ perfluoroalkylene group which may have an ethericoxygen atom. The perfluoroalkylene group may be linear or branched. Thefollowing are preferred with a view to sufficiently imparting initialwater/oil repellency, abrasion resistance and fingerprint stainremovability to the surface-treated layer.

—CF₂CF₂OCF₂CF₂—,

—CF₂CF₂OCF₂CF₂CF₂—,

—CF₂CF₂OCF₂CF₂CF₂OCF₂CF₂—,

—CF₂CF₂OCF₂CF(CF₃)OCF₂CF₂—,

—CF₂CF₂OCF₂CF₂CF₂CF₂OCF(CF₃)—.

L is a hydrolysable group. The hydrolysable group is a group whichbecomes a hydroxy group by a hydrolytic reaction. That is, Si-L at theterminal of the compound (1) becomes a silanol group (Si—OH) by ahydrolytic reaction. Silanol groups are further intermolecularly reactedto form a Si—O—Si bond. Further, silanol groups will undergo adehydration condensation reaction with hydroxy groups (substrate-OH) onthe surface of a substrate to form chemical bonds (substrate-O—Si). Thecompound (1) has a hydrolysable silyl group at its terminal, whereby itsadhesion to a substrate is good, and it is a compound excellent inabrasion resistance and capable of imparting water/oil repellency to thesurface of the substrate.

L may, for example, be an alkoxy group, a halogen atom, an acyl group,an isocyanate group (—NCO) or the like. The alkoxy group is preferably aC₁₋₄ alkoxy group.

L is preferably a C₁₋₄ alkoxy group or a halogen atom, whereby anindustrial production is easy. The halogen atom is particularlypreferably a chlorine atom. L is preferably a C₁₋₄ alkoxy group, wherebygas emission during coating is little, and the compound (1) will beexcellent in the storage stability. In a case where a long term storagestability of the compound (1) is required, an ethoxy group isparticularly preferred, and in a case where it is desired to shorten thereaction time after coating, a methoxy group is particularly preferred.

R is a hydrogen atom or a monovalent hydrocarbon group. The monovalenthydrocarbon group may, for example, be an alkyl group, a cycloalkylgroup, an alkenyl group, an allyl group or the like.

R is preferably a monovalent hydrocarbon group, particularly preferablya monovalent saturated hydrocarbon group. The number of carbon atoms inthe monovalent saturated hydrocarbon group is preferably from 1 to 6,more preferably from 1 to 3, particularly preferably 1 or 2.

From such a viewpoint that the synthesis is easy, R is preferably a C₁₋₆alkyl group, more preferably a C₁₋₃ alkyl group, particularly preferablya C₁₋₂ alkyl group.

k is an integer of at least 1, preferably an integer of from 2 to 6,particularly preferably 3. In a case where k is at least 3, C_(k)H_(2k)may be linear or branched, but is preferably linear.

m is an integer of from 1 to 3, preferably 2 or 3, particularlypreferably 3. By the presence of a plurality of L in one molecule, thebonding to the surface of a substrate will be further strengthened.

When m is at least 2, a plurality of L present in one molecule may bethe same or different from one another. They are preferably the same oneanother from the viewpoint of availability of raw material or productionefficiency.

The hydrolysable silyl group (—SiL_(m)R_(3-m)) is preferably —Si(OCH₃)₃,—SiCH₃(OCH₃)₂, —Si(OCH₂CH₃)₃, —SiCl₃, —Si(OCOCH₃)₃, or —Si(NCO)₃. Fromthe viewpoint of handling efficiency in the industrial production,—Si(OCH₃)₃ is particularly preferred.

Preferred Embodiments

As the compound (1), preferred is a compound having the above-mentionedpreferred A and the above-mentioned preferred chain (αβ) combined, andparticularly preferred are compounds represented by the followingformulae. In the formula number, H means that X in the formula (1-1) isa hydrogen atom, and F means that X in the formula (1-1) is a fluorineatom. The compounds represented by the following formulae are easy toindustrially produce and easy to handle, and can sufficiently impartinitial water/oil repellency, abrasion resistance and fingerprint stainremovability to the surface-treated layer.A-O—[{(CF₂CF₂O)_(x11))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CH₂O(CH₂)₃—SiL_(m)R_(3-m)  (1-1Ha),A-O—[{(CF₂CF₂O)_(x11))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O(CH₂)₃—SiL_(m)R_(3-m)  (1-1Fa),A-O—[{(CF₂CF₂O)_(x11))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)NH(CH₂)₃—SiL_(m)R_(3-m)  (1-3a),A-O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂CH₂O(CH₂)₃—SiL_(m)R_(3-m)  (1-1Hb),A-O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O(CH₂)₃—SiL_(m)R_(3-m)  (1-1Fb),A-O-[{(CF₂O)_(x12)(CF₂CF₂O)_(x13))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)NH(CH₂)₃—SiL_(m)R_(3-m)  (1-3b),CF₃(CF₂)₂—O—[{(CF₂CF₂CF₂O)_(x14))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x23)}]—CF₂CF₂OCF₂CF₂CF₂CH₂O(CH₂)₃—SiL_(m)R_(3-m)  (1Hc),CF₃(CF₂)₂—O—[{(CF₂CF₂CF₂O)_(x14))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x23)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O(CH₂)₃—SiL_(m)R_(3-m)  (1-1Fc),CF₃(CF₂)₂—O—[{(CF₂CF₂CF₂O)_(x14))}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x23)}]—CF₂CF₂OCF₂CF₂CF₂CONH(CH₂)₃—SiL_(m)R_(3-m)  (1-3c).

Here, A is CF₃—, CF₃CF₂— or CF₃(CF₂)₂—.

[Method for Producing Fluorinated Ether Compound]

A compound (1) wherein B is a group represented by the formula (2-1) or(2-2), can be produced by a method of introducing a hydrolysable silylgroup at a terminal via a step of hydrosilylating a precursor (3)represented by the following formula (3).A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)CX₂O—CH₂CH═CH₂  (3)

When the compound (1) is produced via a step of hydrosilylating theprecursor (3), a compound (1-1) wherein B is a group represented by theformula (2-1) is obtainable, and at the same time, a compound (1-2)wherein B is a group represented by the formula (2-2) is obtainable as abyproduct. For example, by subjecting the precursor (3) andHSiL_(m)R_(3-m) (wherein L and R are the same types of the atom or groupas in the formula (1), and m is the same numerical value as in theformula (1)) to a hydrosilylation reaction, it is possible to obtain thecompounds (1-1) and (1-2). It is preferred to carry out thehydrosilylation reaction by means of a transition metal catalyst such asplatinum (Pt) or a radical generating agent such as an organic peroxide.

A compound (1) wherein B is a group represented by the formula (2-3),can be produced by a method of introducing a hydrolysable silyl group ata terminal via a step of reacting a precursor (4) represented by thefollowing formula (4) and an aminoalkyl silane compound. In the formula(4), R¹ is an alkyl group, and from the viewpoint of easy synthesis, aC₁₋₃ alkyl group is preferred.A-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—R^(f4)C(═O)OR¹  (4)

For example, by an amidation reaction of the precursor (4) andH₂NC_(k)H_(2k)SiL_(m)R_(3-m) (wherein L and R are the same types of theatom or group as in the formula (1), and m and k are the same numericalvalues as in the formula (1)), it is possible to obtain the compound(1-3).

The precursor (3) or (4) can be produced by a known method dependingupon the structure ofA-O—[{(R^(f1)O)_(x1)}{(R^(f2)O)_(x2)(R^(f3)O)_(x3)}]—. The method forproducing the precursor (3) or (4) is as follows.

[Method for Producing Precursor (3)]

The method for producing the precursor (3) will be described withreference to the case of a precursor (3a) represented by the followingformula (3a).A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CX₂O—CH₂CH═CH₂  (3a)

Hereinafter, the case where X in the formula (3a) is a fluorine atom,will be referred to as a precursor (3Fa), and the case where X is ahydrogen atom, will be referred to as a precursor (3Ha), and examples ofthe respective production methods will be described.A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O—CH₂CH═CH₂  (3Fa)A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CH₂O—CH₂CH═CH₂  (3Ha)<Method (i) for Producing Precursor (3Fa)>

A compound (7a) represented by the following formula (7a) is heated inthe presence of a metal fluoride catalyst (such as NaF, CsF, KF or AgF)to carry out pyrolysis of the ester, and then allyl bromide(Br—CH₂CH═CH₂) is reacted to obtain a precursor (3Fa). In the formula(7a), R^(f5) is a perfluoroalkyl group or a C₂₋₁₁ perfluoroalkyl grouphaving an etheric oxygen atom.A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O—C(═O)R^(f5)  (7a)<Method (ii) for Producing Precursor (3Fa)>

The precursor (3Fa) can be produced also by the following method.

A compound (8a) represented by the following formula (8a) is reactedwith allyl bromide (Br—CH₂CH═CH₂) in the presence of a metal fluoridecatalyst (such as NaF, CsF, KF or AgF) to obtain a precursor (3Fa).A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)F  (8a)<Method for Producing Precursor (3Ha)>

An alcohol (such as methanol, ethanol, 1-propanol or 2-propanol,hereinafter referred to as R²OH wherein R² is an alkyl group) is reactedto the compound (7a) or (8a) to obtain a compound (6a) represented bythe following formula (6a).A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)OR²  (6a)

Then, the compound (6a) is subjected to hydrogen reduction by means of areducing agent (such as sodium boron hydride or aluminum lithiumhydride) to obtain a compound (5a) represented by the following formula(5a).A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂CH₂OH  (5a)

The obtained compound (5a) is reacted with allyl bromide (Br—CH₂CH═CH₂)in the presence of a base (such as sodium hydride,tert-butoxy-potassium, sodium hydroxide or potassium hydroxide) toobtain the precursor (3Ha).

(Method for Producing Precursor (4))

The method for producing the precursor (4) will be described withreference to the case of a precursor (4a) represented by the followingformula (4a).A-O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)OR¹  (4a)<Method for Producing Precursor (4a)>

The precursor (4a) is the same compound as the compound (6a) except thatR¹ and R² are different. As mentioned above, it can be produced byreacting an alcohol to the compound (7a) or (8a).

<Method for Producing Compound (7a)>

The method for producing the compound (7a) will be described withreference to a case where —R^(f5) is —CF(CF₃)O(CF₂)₂CF₃.

In accordance with a known method disclosed in U.S. Pat. No. 5,134,211,a compound (12a) represented by the following formula (12a) issynthesized from a compound (13a) represented by the following formula(13a).CF₂═CFO—CF₂CF₂CF₂COOCH₃  (13a)CF₂═CFO—CF₂CF₂CF₂CH₂OH  (12a)

In accordance with a known method disclosed in WO2009/008380, a compound(11a) represented by the following formula (11a) is obtained.A-O—(CF₂CF₂O)_(x11-1)—CF₂CH₂OH  (11a)

The compound (12a) and the compound (11a) are reacted in the presence ofa base or a quaternary ammonium salt (such as potassium carbonate,sodium carbonate, sodium fluoride, potassium fluoride, cesium fluoride,sodium hydride, tert-butoxy potassium, sodium hydroxide, potassiumhydroxide, tetrabutyl ammonium chloride or tetrabutyl ammonium bromide)to obtain an oligomer compound (10a) represented by the followingformula (10a).A-O—[{(CF₂CF₂O)_(x11-1)—CF₂CH₂O}—{(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(x21+1)}]—H  (10a)

By controlling the amount of the compound (11a) to be added to thecompound (12a), it is possible to synthesize an oligomer compound (10a)having a desired number average molecular weight.

The synthesis of the compound (10a) by the polyaddition reaction can becarried out by known method disclosed in U.S. Pat. No. 5,134,211.

By an esterification reaction of the compound (10a) andCF₃CF₂CF₂OCF(CF₃)COF, a compound (9a) represented by the followingformula (9a) is obtained. Such an esterification reaction is not limitedto the reaction of the compound (10a) with a perfluoro-acid fluoride asin the above example, and may be a reaction with a fluorinated ornon-fluorinated hydrocarbon type acid fluoride, acid chloride, acidbromide or acid anhydride.A-O—[{(CF₂CF₂O)_(x11-1)—CF₂CH₂O}—{(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(x21+1)}]—C(═O)CF(CF₃)OCF₂CF₂CF₃  (9a)

Further, by means of fluorine gas, hydrogen atoms in the compound (9a)may be substituted by fluorine atoms to obtain the compound (7a). Such afluorination step can be carried out, for example, in accordance with amethod disclosed in WO2000/56694.

[Fluorinated Ether Composition]

The fluorinated ether composition of the present invention (hereinafterreferred to as the present composition) is a composition containing atleast 95 mass % of the present compound.

The present composition may contain impurities other than the presentcompound. The impurities other than the present compound mean compoundsunavoidable in the production of the present compound. Specifically,they are byproducts formed in the production steps for the presentcompound and components included in the production steps for the presentcompound. The present composition does not contain the after-describedliquid medium. The content of impurities other than the present compoundin the present composition is preferably at most 5 mass %.

The content of the present compound in the present composition isparticularly preferably at least 98 mass %. That is, the content ofimpurities is particularly preferably at most 2 mass %. When the contentof the present compound is within such a range, the initial water/oilrepellency, abrasion resistance and fingerprint stain removability willbe excellent when used for surface treatment of a substrate.

Identification and quantitative determination of byproducts in thepresent composition are carried out by means of ¹H-NMR (300.4 MHz) and¹⁹F-NMR (282. 7 MHz). For example, in a case where the desired compounds(1-1) and (1-2) are to be produced via a step of hydrosilylation of theprecursor (3), a byproduct will be formed by the hydrosilylation. A casewhere no spectral peak attributable to such a byproduct (a compound ofthe formula (1) wherein B is represented by the following formula (2-5))is detected, is defined that the content of the byproduct is zero. Here,in a case where a spectral peak attributable to the byproduct isobserved, the content of the byproduct is obtained by quantitativedetermination by means of an internal standard.—R^(f4)CX₂O—CH═CHCH₃  (2-5)[Method for Producing Substrate Having Surface-Treated Layer](Dry Coating Method)

The present compound and the present composition can be used as they arefor a method for producing a substrate having a surface-treated layer,by treating the surface of the substrate by a dry coating method. Thepresent compound and the present composition are suitable to form asurface-treated layer excellent in the adhesion by a dry coating method.The dry coating method may, for example, be a technique such as vacuumdeposition, CVD or sputtering. A vacuum deposition method can besuitably used with a view to preventing decomposition of the presentcompound and in view of simplicity of the apparatus. The vacuumdeposition method can be classified into a resistance heating method, anelectron beam heating method, a high frequency induction heating method,a reactive deposition method, a molecular beam epitaxy method, a hotwall deposition method, an ion plating method, a cluster ion beammethod, etc., and any method can be used. A resistance heating methodcan be suitably used with a view to preventing decomposition of thepresent compound and in view of simplicity of the apparatus. The vacuumdeposition apparatus is not particularly limited, and a known apparatusmay be used.

In a case where a vacuum deposition method is employed, the filmdeposition conditions vary depending upon the type of the vacuumdeposition method to be applied, and in the case of a resistance heatingmethod, the degree of vacuum before deposition is preferably at most1×10⁻² Pa, particularly preferably at most 1×10⁻³ Pa. The heatingtemperature of the deposition source is not particularly limited so longas it is a temperature at which the present compound or the presentcomposition used as the deposition source has a sufficient vaporpressure. It is specifically preferably from 30 to 400° C., particularlypreferably from 50 to 300° C. When the heating temperature is at leastthe lower limit value of the above range, the film deposition rate willbe good. When it is at most the upper limit value of the above range, itis possible to impart initial water/oil repellency, abrasion resistanceand fingerprint stain removability to the substrate surface withoutcausing decomposition of the present compound.

At the time of vacuum deposition, the substrate temperature ispreferably within a range of from room temperature (20 to 25° C.) to200° C. When the substrate temperature is at most 200° C., the filmdeposition rate will be good. The upper limit value of the substratetemperature is more preferably at most 150° C., particularly preferablyat most 100° C.

In a case where the surface of a substrate is treated by a dry coatingmethod using the present compound or the present composition, thesurface-treated layer to be formed on the surface of the substrate bythe treatment has a film thickness of preferably from 1 to 100 nm,particularly preferably from 1 to 50 nm. When the film thickness of thesurface-treated layer is at least the lower limit value of the aboverange, the effect by the surface treatment is readily sufficientlyobtainable. When it is at most the upper limit value of the above range,the utilization efficiency tends to be high. To measure the filmthickness, for example, an interference pattern of reflected X-rays isobtained by an X-ray reflectance method using an X-ray diffractometerfor thin-film analysis ATX-G (manufactured by Rigaku Corporation), andfrom the oscillation period of the interference pattern, the filmthickness can be calculated.

Particularly, in the vacuum deposition method, the effect to improve theinitial water/oil repellency, abrasion resistance and fingerprint stainremovability is large, since the content of the present compound in thepresent composition is large, and the content of impurities is small.This is considered to be such that it is thereby possible to preventvapor deposition of byproducts having small molecular weights, asimpurities, on the surface of a substrate, prior to the presentcompound, to hinder chemical bonds between the surface of the substrateand the present compound to provide the effect.

(Wet Coating Method)

A substrate having a surface-treated layer can be produced by applying acoating liquid containing the present compound to the surface of asubstrate, followed by drying.

As a method for applying the coating liquid, a known technique maysuitably be employed.

The application method is preferably a spin coating method, a wipecoating method, a spray coating method, a squeegee coating method, a dipcoating method, a die coating method, an ink jet method, a flow coatingmethod, a roll coating method, a casting method, a Langmuir-Blodgettmethod or a gravure coating method.

The method for drying may be any method so long as it is capable ofdrying and removing the medium, and a known technique may suitably beemployed. The temperature for drying is preferably from 10 to 300° C.,particularly preferably from 20 to 200° C.

The surface-treated layer to be formed on the surface of the substrateafter the medium is dried and removed has a film thickness of preferablyfrom 1 to 100 nm, particularly preferably from 1 to 50 nm. When the filmthickness of the surface-treated layer is at least the lower limit valueof the above range, the effect by the surface treatment is readilysufficiently obtainable. When it is at most the upper limit value of theabove range, the utilization efficiency tends to be high. Measurement ofthe film thickness can be carried out in the same manner as the methodof measuring the film thickness of the surface-treated layer formed by adry coating method.

(Post Treatment)

At the time of producing a substrate having a surface-treated layer byeither one of the above methods, in order to improve the durabilityagainst abrasion of the surface-treated layer, an operation to promotethe reaction of the hydrolysable silyl groups with the substrate may becarried out as the case requires. Such an operation may, for example, beheating, humidification or light irradiation.

After the surface treatment, a compound in the surface-treated layerwhich is not chemically bonded to another compound or the substrate, maybe removed as the case requires. As a specific method, for example, amethod of washing the surface-treated layer with a solvent, or a methodof wiping the surface-treated layer with cloth impregnated with asolvent, may be mentioned.

(Coating Liquid)

The coating liquid of the present invention (hereinafter referred to asthe present coating liquid) contains the present compound and a medium.The medium is preferably liquid. The present coating liquid is in aliquid form and may be a solution or a dispersion.

The present coating liquid contains the present compound and may containimpurities such as byproducts formed in the production steps for thepresent compound. Accordingly, the present coating liquid may containthe present composition and a medium.

The concentration of the present compound is preferably from 0.001 to 10mass %, particularly preferably from 0.1 to 1 mass % in the presentcoating liquid.

<Medium>

The medium is preferably an organic solvent. The organic solvent may bea fluorinated organic solvent or a non-fluorinated organic solvent, ormay contain both solvents.

The fluorinated organic solvent may, for example, be a fluorinatedalkane, a fluorinated aromatic compound, a fluoroalkyl ether, afluorinated alkylamine or a fluoroalcohol.

The fluorinated alkane is preferably a C₄₋₈ compound. As commerciallyavailable products, for example, C₆F₁₃H (AC-2000, tradename,manufactured by Asahi Glass Company, Limited), C₆F₁₃C₂H₅ (AC-6000,tradename, manufactured by Asahi Glass Company, Limited) andC₂F₅CHFCHFCF₃ (Vertrel, tradename, manufactured by Du Pont KabushikiKaisha) may, for example, be mentioned.

The fluorinated aromatic compound may, for example, behexafluorobenzene, trifluoromethylbenzene, perfluorotoluene orbis(trifluoromethyl)benzene.

The fluoroalkyl ether is preferably a C₄₋₁₂ compound. As commerciallyavailable products, for example, CF₃CH₂OCF₂CF₂H (AE-3000, tradename,manufactured by Asahi Glass Company, Limited), C₄F₉OCH₃ (Novec-7100,tradename, manufactured by Sumitomo 3M Limited), C₄F₉OCH₅ (Novec-7200,tradename, manufactured by Sumitomo 3M Limited) and C₆F₁₃OCH₃(Novec-7300, tradename, manufactured by Sumitomo 3M Limited) may, forexample, be mentioned.

The fluorinated alkylamine may, for example, be perfluorotripropylamineor perfluorotributylamine.

The fluoroalcohol may, for example, be 2,2,3,3-tetrafluoropropanol,2,2,2-trifluoroethanol or hexafluoroisopropanol.

The fluorinated organic solvent is preferably a fluorinated alkane, afluorinated aromatic compound or a fluoroalkyl ether in view of thesolubility of the present compound, and particularly preferred is afluoroalkyl ether.

The non-fluorinated organic solvent is preferably a compound composedsolely of hydrogen atoms and carbon atoms or a compound composed solelyof hydrogen atoms, carbon atoms and oxygen atoms, and may, for example,be a hydrocarbon organic solvent, an alcohol organic solvent, a ketoneorganic solvent, an ether organic solvent or an ester organic solvent.

The hydrocarbon organic solvent is preferably hexane, heptane,cyclohexane or the like.

The alcohol organic solvent is preferably methanol, ethanol, propanol,isopropanol or the like.

The ketone organic solvent is preferably acetone, methyl ethyl ketone,methyl isobutyl ketone or the like.

The ether organic solvent is preferably diethyl ether, tetrahydrofuran,tetraethylene glycol dimethyl ether or the like.

The ester organic solvent is preferably ethyl acetate, butyl acetate orthe like.

The non-fluorinated organic solvent is particularly preferably a ketoneorganic solvent in view of the solubility of the present compound.

The medium is preferably at least one organic solvent selected from thegroup consisting of the fluorinated alkane, the fluorinated aromaticcompound, the fluoroalkyl ether, the compound composed solely ofhydrogen atoms and carbon atoms and the compound composed solely ofhydrogen atoms, carbon atoms and oxygen atoms. Particularly preferred isa fluorinated organic solvent selected from the fluorinated alkane, thefluorinated aromatic compound and the fluoroalkyl ether.

The medium preferably contains at least one organic solvent selectedfrom the group consisting of the fluorinated alkane, the fluorinatedaromatic compound, the fluoroalkyl ether, as fluorinated organicsolvents, the compound composed solely of hydrogen atoms, carbon atomsand oxygen atoms, as non-fluorinated solvents, in a total amount of atleast 90 mass %, based on the entire medium with a view to increasingthe solubility of the present compound.

The present coating liquid contains preferably from 90 to 99.999 mass %,particularly preferably from 99 to 99.99 mass %, of the medium.

The present coating liquid may contain other components in addition tothe present compound and the medium, within a range not to impair theeffects of the present invention.

Such other components may, for example, be known additives such as anacid catalyst or a basic catalyst, which promotes hydrolysis of thehydrolyzable silyl group and a condensation reaction, etc.

The acid catalyst may, for example, be hydrochloric acid, nitric acid,acetic acid, sulfuric acid, phosphoric acid, sulfonic acid,methanesulfonic acid or p-toluenesulfonic acid.

The basic catalyst may, for example, be sodium hydroxide, potassiumhydroxide or ammonia.

In the present coating liquid, the content of other components ispreferably at most 10 mass %, particularly preferably at most 1 mass %.

The solid content concentration of the present coating liquid ispreferably from 0.001 to 10 mass %, particularly preferably from 0.01 to1 mass %. The solid content concentration of the coating liquid is avalue calculated from the mass of the coating liquid before heating andthe mass after the coating liquid is heated by a convection dryer at120° C. for 4 hours. Further, the concentration of the presentcomposition can be calculated from the solid content concentration andthe amounts of charge of the present composition, the medium, etc.

(Substrate)

In the present invention, the substrate to be subjected to surfacetreatment is not particularly limited so long as it is a substrate towhich the water/oil repellency is required to be imparted. The materialof the surface of the substrate may, for example, be a metal, a resin,glass, a ceramic or a composite material thereof.

By surface treatment of the substrate using the present compound, thepresent composition containing it or the present coating liquid to forma surface-treated layer, good initial water/oil repellency is impartedand at the same time, excellent abrasion resistance whereby thewater/oil repellency is hardly decreased even by repeated abrasion ofthe surface, and a performance (fingerprint stain removability) wherebya fingerprint stain on the surface of a substrate can easily be removed,are obtainable. Accordingly, the substrate having a surface-treatedlayer thus obtained, has good initial water/oil repellency and also hasexcellent abrasion resistance and fingerprint stain removability,whereby it is useful as a member constituting a touch panel. A touchpanel means an input device of an input/display device (touch paneldevice) comprising a device to input contact location information bycontact by e.g. fingers and a display device in combination. The touchpanel comprises a substrate, and depending upon the input detectionmethod, a transparent electrically conductive membrane, an electrode, awiring, an IC, etc. A touch panel having good fingerprint stainremovability can be obtained by disposing the substrate so that itssurface having a surface-treated layer becomes an input screen of thetouch panel.

The material of the substrate for a touch panel has translucency. Here,“has translucency” means that the normal incidence visible lighttransmittance in accordance with JIS R3106 is at least 25%.

The material of the substrate for a touch panel is preferably glass or atransparent resin. The glass is preferably soda lime glass, alkalialuminosilicate glass, borosilicate glass, alkali-free glass, crystalglass or quartz glass, particularly preferably chemically tempered sodalime glass, chemically tempered alkali aluminosilicate glass orchemically tempered borosilicate glass. The transparent resin substrateis preferably an acrylic resin or polycarbonate.

Further, the substrate in the present invention is also preferably asubstrate for a display constituting the outermost surface of a displaysuch as a liquid crystal display, a CRT display, a projection display, aplasma display or an EL display, and by forming a surface-treated layerby surface treatment using the present compound, the present compositionor the present coating liquid, good fingerprint stain removability willbe obtained.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples. In thefollowing, “%” means “mass %” unless otherwise specified. Ex. 1, 3, 11and 13 are Examples of the present invention, and Ex. 2 and 12 areComparative Examples.

Ex. 1 Production of Composition (A) Ex. 1-1

Into a 300 mL three-necked round-bottomed flask, 14.1 g of a sodiumborohydride powder was put, and 350 g of AK-225 (trade name,manufactured by Asahi Glass Company, Limited) was added. While coolingand stirring in an ice bath, a solution having 100 g of a compound(13a), 15.8 g of methanol and 22 g of AK-225 mixed, was slowly dropwiseadded in a nitrogen atmosphere so that the internal temperature wouldnot exceed 10° C. After dropwise addition of the entire amount, asolution having 10 g of methanol and 10 g of AK-225 mixed, was dropwiseadded. Then, the ice bath was removed, and while raising the temperatureslowly to room temperature, stirring was continued. After stirring atroom temperature for 12 hours, the reaction mixture was cooled again inan ice bath, and an aqueous hydrochloric acid solution was dropwiseadded until the liquid became acidic. After termination of the reaction,the reaction mixture was washed once with water and once with asaturated aqueous sodium chloride solution, whereupon an organic phasewas recovered. The recovered organic phase was dried over magnesiumsulfate, and then, the solid content was filtered off, and the filtratewas concentrated by an evaporator. The recovered concentrated liquid wasdistilled under reduced pressure to obtain 80.6 g (yield: 88%) of thecompound (12a).CF₂═CFO—CF₂CF₂CF₂COOCH₃  (13a)CF₂═CFO—CF₂CF₂CF₂CH₂OH  (12a)NMR Spectrum of Compound (12a):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 2.2 (1H), 4.1 (2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −85.6 (2F), −114.0 (1F), −122.2 (1F), −123.3 (2F), −127.4 (2F),−135.2 (1F).

Ex. 1-2

In accordance with the known method disclosed in WO2009/008380, acompound (11a-1) represented by the following formula (11a-1) wasobtained.CF₃—O—(CF₂CF₂O)_(x11-1)—CF₂CH₂OH  (11a-1)

Ex. 1-3

Into a 100 mL eggplant flask connected to a reflux condenser, 22.0 g ofthe compound (12a) obtained in Ex. 1-1, and 10.0 g of the compound(11a-1) obtained in Ex. 1-2 were introduced, and 1.47 g of a potassiumcarbonate powder was added. After stirring at 60° C. for 8 hours in anitrogen atmosphere, 1.74 g of potassium carbonate powder wasadditionally added, followed by stirring at 80° C. for 2 hours, andfurther at room temperature for 24 hours. Excess potassium carbonate wastreated by adding an aqueous hydrochloric acid solution, and water andAK-225 were added to carry out liquid separation treatment. Afterwashing with water three times, the organic phase was recovered andconcentrated by an evaporator to obtain 32.65 g of an oligomer with ahigh viscosity. It was diluted again with 30 g of AK-225 and developedand fractionated by silica gel column chromatography (developingsolvent: AK-225). With respect to each fraction, an average value of(x21+1) in the formula (10a-1) was obtained from the integrated value of¹⁹F-NMR. 6.06 g of a compound (10a-1) having fractions with an averagevalue of (x21+1) being from 7 to 15 put together, was obtained.CF₃—O—[{(CF₂CF₂O)_(x11-1)—CF₂CH₂O}—{(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(x21+1)}]—H  (10a-1)NMR Spectrum of Compound (10a-1):

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):4.1 (2H), 4.8 (22H), 6.7-6.9 (11H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −55.3 (3F), −77.6 (2F), −83.7˜−85.1 (22F), −88.5 (24F),−89.3˜−90.4 (22F), −120.2 (20F), −122.0 (2F), −126.6 (22F), −145.1(11F).

Average value of (x11−1): 6

Average value of (x21+1): 11

Ex. 1-4

Into a 50 mL eggplant flask connected to a reflux condenser, 8.06 g ofthe compound (10a-1) obtained in Ex. 1-3, 0.55 g of a sodium fluoridepowder and 16 g of AK-225 were introduced, and 9.32 g ofCF₃CF₂CF₂OCF(CF₃)COF was added. After stirring at 40° C. for 14 hours ina nitrogen atmosphere, the sodium fluoride powder was removed bypressure filtration, and then, excess CF₃CF₂CF₂OCF(CF₃)COF and AK-225were distilled off under reduced pressure. By silica gel columnchromatography (developing solvent: AK-225), highly polar impuritieswere removed to obtain 7.81 g (yield: 89%) of a compound (9a-1).CF₃—O—[{(CF₂CF₂O)_(x11-1)—CF₂CH₂O}—{(CF₂CFHO—CF₂CF₂CF₂CH₂O)_(x21+1)}]—C(═O)CF(CF₃)OCF₂CF₂CF₃  (9a-1)NMR Spectrum of Compound (9a-1):

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):4.8 (22H), 5.2 (2H), 6.7-6.9 (11H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −55.2 (3F), −77.6 (2F), −76.5˜−77.6 (1F), −79.4 (3F), −81.1 (3F),−83.7˜−85.0 (22F), −85.7˜−86.3 (1F), −88.5 (24F), −89.0˜−91.8 (22F),−119.8 (2F), −120.2 (20F), −126.6 (22F), −129.3 (2F), −131.5 (1F),−145.1 (11F).

Average value of (x11−1): 6

Average value of (x21+1): 11

Ex. 1-5

An autoclave (made of nickel, internal capacity: 1 L) was provided, andat a gas discharge outlet of the autoclave, a condenser held at 0° C., aNaF pellets-packed layer and a condenser held at −10° C. were set inseries. Further, a liquid-returning line to return a liquid condensedfrom the condenser held at −10° C. to the autoclave, was set.

Into the autoclave, 312 g of R-113 (CF₂ClCFCl₂) was put and stirredwhile maintaining the temperature at 25° C. After blowing nitrogen gasat 25° C. for one hour into the autoclave, fluorine gas diluted to 20vol % with nitrogen gas (hereinafter referred to as the 20% fluorinegas), was blown into it at 25° C. for one hour at a flow rate of 1.5L/hr. Then, while blowing the 20% fluorine gas at the same flow rate, asolution having 7.6 g of the compound (9a-1) obtained in Ex. 1-4dissolved in 76 g of R-113, was injected into the autoclave over aperiod of 3.5 hours.

Then, while blowing the 20% fluorine gas at the same flow rate, theinternal pressure of the autoclave was raised to 0.15 MPa (gaugepressure). Into the autoclave, 9 mL of a benzene solution containing0.015 g/mL of benzene in R-113, was injected while heating to from 25°C. to 40° C., whereupon the benzene solution injection inlet of theautoclave was closed. After stirring for 20 minutes, 6 mL of the benzenesolution was injected again while maintaining the temperature at 40° C.,whereupon the injection inlet was closed. The same operation was furtherrepeated 3 times. The total injected amount of benzene was 0.4 g.

Further, stirring was continued for one hour while blowing the 20%fluorine gas at the same flow rate. Then, the internal pressure of theautoclave was adjusted to the atmospheric pressure, and nitrogen gas wasinjected for one hour. The content in the autoclave was concentrated byan evaporator to obtain 8.6 g (yield: 99%) of a compound (7a-1).CF₃—O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂O—CF₂CF₂CF₂CF₂O—C(═O)CF(CF₃)OCF₂CF₂CF₃  (7a-1)NMR Spectrum of Compound (7a-1):

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −56.2 (3F), −79.7˜−80.3 (1F), −82.1 (3F), −82.3 (3F), −83.8(42F), −86.7˜−87.7 (3F), −89.2 (70F), −91.0 (2F), −126.3 (44F), −130.2(2F), −132.4 (1F).

Average value of x11: 7

Average value of x21: 10

Ex. 1-6

Into a 50 mL eggplant flask connected to a reflux condenser, 8.6 g ofthe compound (7a-1) obtained in Ex. 1-5, 0.39 g of a sodium fluoridepowder and 60 g of AK-225 were introduced. While cooling and stirring inan ice bath, 2.14 g of methanol was dropwise added in a nitrogenatmosphere. After stirring at 50° C. for 4 hours in a nitrogenatmosphere, the sodium fluoride powder was removed by pressurefiltration, and the reaction mixture was concentrated by an evaporatorto obtain 7.7 g (yield: 96%) of a precursor (4a-1).CF₃—O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)OCH₃  (4a-1)NMR Spectrum of Compound (4a-1):

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):3.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −56.5 (3F), −84.2 (42F), −89.4 (70F), −91.5 (2F), −119.5 (2F),−126.6 (40F), −127.5 (2F).

Average value of x11: 7

Average value of x21: 10

Ex. 1-7

Into a 6 mL screw bottle, 2.0 g of the precursor (4a-1) obtained in Ex.1-6 and 0.11 g of H₂NCH₂CH₂CH₂Si(OCH₃)₃ were put and stirred for 12hours. From NMR, it was confirmed that 97% of the precursor (4a-1) wasconverted to a compound (1-3a-1). Further, all of H₂NCH₂CH₂CH₂Si(OCH₃)₃was reacted, and methanol was formed as a byproduct. Thus, a composition(A) containing 96% of the compound (1-3a-1) was obtained. The numberaverage molecular weight of the compound (1-3a-1i) was 4,700. Theresults are shown in Table 1.CF₃—O—[{(CF₂CF₂O)_(x11)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x21)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)NHCH₂CH₂CH₂—Si(OCH₃)₃  (1-3a-1)NMR Spectrum of Compound (1-3a-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 0.6 (2H), 1.6 (2H), 2.8 (1H), 3.3 (2H), 3.5 (9H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −56.3 (3F), −84.1 (42F), −89.3 (70F), −91.4 (2F), −120.8 (2F),−126.5 (40F), −127.6 (2F).

Average value of x11: 7

Average value of x21: 10

Ex. 2 Production of Compound (B)

A fluorinated ether compound constituted by a combination of (CF₂O) and(CF₂CF₂O) was synthesized in accordance with the method disclosed inU.S. Pat. No. 5,258,110 and U.S. Pat. No. 3,847,978. The acid fluoride(—COF) terminal of the obtained fluorinated ether compound wasesterified by a reaction with an alcohol, and an aminopropylsilanecompound was reacted to convert the terminal to a hydrolysabletrimethoxysilyl group thereby to obtain the compound (B).

Ex. 3 Production of Composition (C) Ex. 3-1

Into a 500 mL three-necked round-bottomed flask, 1.04 g of potassiumhydroxide was put, and 83 g of tert-butanol and 125 g of1,3-bis(trifluoromethyl)benzene were added. The potassium hydroxide wasdissolved with stirring at room temperature, and 250 g of FLUOROLINKD10/H (trade name, Solvay Solexis, Inc.) was added thereto, followed bystirring for one hour. At room temperature, 38.2 g of the compound (14)was added, and stirring was continued for further 24 hours. An aqueoushydrochloric acid was added for neutralization, and water was furtheradded to carry out liquid separation treatment. After washing with waterthree times, the organic phase was recovered and concentrated by anevaporator to obtain 288.0 g of a reaction crude liquid. It was dilutedagain with 144 g of AC-2000 and developed and fractionated by silica gelcolumn chromatography (developing solvent: AC-2000 and AE-3000). Thus,136.2 g (yield: 47%) of a compound (11b-1) having the compound (14)added only to its molecular terminal, was obtained.CF₂═CF—O—CF₂CF₂CF₃  (14)CF₃(CF₂)₂—O—CHFCF₂—O—CH₂CF₂—O—(CF₂O)_(x12)(CF₂CF₂O)_(x13-3)—CF₂CH₂OH  (11b-1)NMR Spectrum of Compound (11b-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 3.9 (2H), 4.2 (2H), 5.9 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −52.3˜−55.7 (14F), −78.7 (1F), −80.7 (1F), −81.3 (1F), −82.1(3F), −83.4 (1F), −85.3˜−88.2 (2F), −89.4˜−91.1 (38F), −130.5 (2F),−145.2 (1F).

Average value of x12: 8

Average value of x13−3: 10

Ex. 3-2

Into a 200 mL eggplant flask connected to a reflux condenser, 80.0 g ofthe compound (11b-1) obtained in Ex. 3-1, was introduced, and 3.26 g ofa potassium carbonate powder was added. In a nitrogen atmosphere, thetemperature was raised to 120° C., 110.7 g of the compound (12a)obtained in Ex. 1-1 was slowly dropwise added while controlling so thatthe internal temperature would be at most 130° C. After dropwise addingthe entire amount, stirring was continued for further one hour whilemaintaining the temperature at 120° C., whereupon heating was stopped,and stirring was continued until the temperature lowered to roomtemperature. Excess potassium carbonate was treated by adding an aqueoushydrochloric acid solution, and water and AK-225 were added to carry outliquid separation treatment. After washing with water three times, theorganic phase was recovered and concentrated by an evaporator to obtain183.7 g of an oligomer with a high viscosity. It was diluted again with110 g of AC-2000 and developed and fractionated by silica gel columnchromatography (developing solvent: AC-2000 and AE-3000). With respectto each fraction, an average value of (x22+1) in the following formula(10b-1) was obtained from the integrated value of ¹⁹F-NMR. 83.5 g of acompound (10b-1) having fractions with an average value of (x22+1) beingfrom 6 to 9 put together, was obtained.CF₃(CF₂)₂—O—CHFCF₂—O—CH₂CF₂—O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13-3)—CF₂CH₂O}—{(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x22+1)}]—H  (10b-1)NMR Spectrum of Compound (10b-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 4.0 (2H), 4.2 (4H), 4.4 (12H), 5.9 (8H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −52.4˜−55.8 (16F), −78.8 (2F), −80.8 (2F), −82.2 (3F),−84.7˜−88.2 (16F), −89.4˜−92.2 (56F), −121.5 (12F), −123.7 (2F), −128.0(14F), −130.5 (2F), −145.0 (8F).

Average value of x12: 8

Average value of x13−3: 10

Average value of x22+1: 7

Ex. 3-3

Into a 100 mL eggplant flask connected to a reflux condenser, 80.1 g ofthe compound (10a-1b) obtained in Ex. 3-2, was introduced, and 7.63 g ofacetic acid chloride was added. In a nitrogen atmosphere, stirring wascarried out at 40° C. for 12 hours, whereupon excess acetic acidchloride was distilled off under reduced pressure. Highly polarimpurities were removed by silica gel column chromatography (developingsolvent: AK-225) to obtain 79.7 g (yield: 98%) of a compound (9b-1) wasobtained.CF₃(CF₂)₂—O—CHFCF₂—O—CH₂CF₂—O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13-3)—CF₂CH₂O}—{(CF₂CHFO—CF₂CF₂CF₂CH₂O)_(x22+1)}]—C(═O)CH₃  (9b-1)NMR Spectrum of Compound (9b-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 2.1 (3H), 4.2 (4H), 4.4 (12H), 4.5 (2H), 5.9 (8H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −52.4˜−55.8 (16F), −78.8 (2F), −80.8 (2F), −82.2 (3F),−84.7˜−88.2 (16F), −89.4˜−92.2 (56F), −120.9 (2F), −121.5 (12F), −128.0(14F), −130.5 (2F), −145.0 (8F).

Average value of x12: 8

Average value of x13−3: 10

Average value of x22+1: 7

Ex. 3-4

An autoclave (made of nickel, internal capacity: 1 L) was provided, andat a gas discharge outlet of the autoclave, a condenser held at 0° C., aNaF pellets-packed layer and a condenser held at −10° C. were set inseries. Further, a liquid-returning line to return a liquid condensedfrom the condenser held at −10° C. to the autoclave, was set.

Into the autoclave, 312 g of ClCF₂CFClCF₂OCF₂CF₂Cl (hereinafter referredto as CFE-419) was put and stirred while maintaining the temperature at25° C. After blowing nitrogen gas at 25° C. for one hour into theautoclave, the 20% fluorine gas was blown into it at 25° C. for one hourat a flow rate of 2.3 L/hr. Then, while blowing the 20% fluorine gas atthe same flow rate, a solution having 75.0 g of the compound (9b-1)obtained in Ex. 3-3 dissolved in 234 g of CFE-419, was injected into theautoclave over a period of 9.0 hours.

Then, while blowing the 20% fluorine gas at the same flow rate, theinternal pressure of the autoclave was raised to 0.15 MPa (gaugepressure). Into the autoclave, 5 mL of a benzene solution containing0.006 g/mL of benzene in CFE-419, was injected while heating to from 25°C. to 40° C., whereupon the benzene solution injection inlet of theautoclave was closed. After stirring for 15 minutes, 5 mL of the benzenesolution was injected again while maintaining the temperature at 40° C.,whereupon the injection inlet was closed. The same operation was furtherrepeated 7 times. The total injected amount of benzene was 0.24 g.

Further, stirring was continued for one hour while blowing the 20%fluorine gas at the same flow rate. Then, the internal pressure of theautoclave was adjusted to the atmospheric pressure, and nitrogen gas wasinjected for one hour. The content in the autoclave was concentrated byan evaporator to obtain 81.5 g (yield: 97%) of a compound (7b-1).CF₃(CF₂)₂—O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂CF₂O—C(═O)CF₃  (7b-1)NMR Spectrum of Compound (7b-1):

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −53.4˜−56.8 (16F), −77.4 (3F), −83.4 (3F), −85.1 (26F), −86.2(2F), −88.3 (2F), −89.9˜−92.1 (80F), −127.5 (28F), −131.8 (2F).

Average value of x12: 8

Average value of x13: 13

Average value of x22: 6

Ex. 3-5

Into a 200 mL eggplant flask connected to a reflux condenser, 80.5 g ofthe compound (7b-1) obtained in Ex. 3-4 and 100 g of AK-225 were put.While cooling and stirring in an ice bath, 3.0 g of methanol wasdropwise added in a nitrogen atmosphere. After stirring at roomtemperature for 4 hours in a nitrogen atmosphere, the reaction mixturewas concentrated by an evaporator to obtain 77.9 g (yield: 99%) of aprecursor (4b-1).CF₃(CF₂)₂—O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)OCH₃  (4b-1)NMR Spectrum of Compound (4b-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 3.9 (3H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −53.3˜−56.7 (16F), −83.3 (3F), −85.0 (26F), −86.1 (2F),−90.0˜−92.0 (80F), −120.4 (2F), −127.4 (24F), −128.4 (2F), −131.7 (2F).

Average value of x12: 8

Average value of x13: 13

Average value of x22: 6

Ex. 3-6

Into a 50 mL eggplant flask, 50.0 g of the precursor (4b-1) obtained inEx. 3-5 and 1.90 g of H₂NCH₂CH₂CH₂Si(OCH₃)₃ were put and stirred for 12hours. From NMR, it was confirmed that 98% of the precursor (4b-1) wasconverted to a compound (1-3b-1). Further, all of H₂NCH₂CH₂CH₂Si(OCH₃)₃was reacted, and methanol was formed as a byproduct. Thus, a composition(C) containing 97% of the compound (1-3b-1), was obtained. The numberaverage molecular weight of the compound (1-3b-1) was 4,700. The resultsare shown in Table 1.CF₃(CF₂)₂—O—[{(CF₂O)_(x12)(CF₂CF₂O)_(x13)}—{(CF₂CF₂O—CF₂CF₂CF₂CF₂O)_(x22)}]—CF₂CF₂OCF₂CF₂CF₂C(═O)NHCH₂CH₂CH₂Si—(OCH₃)₃  (1-3b-1)NMR Spectrum of Compound (1-3b-1):

¹H-NMR (300.4 MHz, solvent: deuterated chloroform, standard: TMS) δ(ppm): 0.5 (2H), 1.6 (2H), 3.2 (2H), 3.4 (9H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated chloroform, standard: CFCl₃) δ(ppm): −53.3˜−56.7 (16F), −83.3 (3F), −85.0 (26F), −86.1 (2F),−90.0˜−92.0 (80F), −121.6 (2F), −127.4 (24F), −128.4 (2F), −131.7 (2F).

Average value of x12: 8

Average value of x13: 13

Average value of x22: 6

Ex. 11 to 13 Production and Evaluation of Substrate HavingSurface-Treated Layer

Using the composition or compound obtained in Ex. 1 to 3, surfacetreatment of a substrate was carried out as Ex. 11 to 13. In each Ex., asubstrate having a surface-treated layer was produced by using each ofthe following dry coating method and wet coating method. As thesubstrate, chemically tempered glass was used. With respect to theobtained substrates having a surface-treated layer, evaluations werecarried out by the following methods. The results are shown in Table 2.

(Dry Coating Method)

The dry coating method was carried out by using a vacuum depositionapparatus (VTR-350M manufactured by ULVAC, Inc.) (vacuum depositionmethod). 0.5 g of the composition or compound obtained in Ex. 1 to 3 wasfilled in a boat made of molybdenum in the vacuum deposition apparatus,and inside of the vacuum deposition apparatus was evacuated to at most1×10⁻³ Pa. The boat having the composition or compound disposed washeated at a heating rate of at most 10° C./min, and at the time when thedeposition rate measured by a quartz film thickness meter exceeded 1nm/sec, a shutter was opened to initiate film deposition on thesubstrate surface. At the time when the film thickness reached about 50nm, the shutter was closed to complete film deposition on the substratesurface. The substrate on which the composition or compound wasdeposited was subjected to heat treatment at 200° C. for 30 minutes andthen washed with AK-225 (trade name, manufactured by Asahi GlassCompany, Limited) which is a fluorinated solvent, to obtain a substratehaving a surface-treated layer.

(Wet Coating Method)

The composition or compound obtained in Ex. 1 to 3 and HFE-7200 (tradename, manufactured by 3M) as a solvent were mixed to prepare a coatingliquid having a solid content concentration of 0.05 mass %. Thesubstrate was dipped in the coating liquid (dip coating method), left tostand for 30 minutes and then pulled out. The substrate was dried at200° C. for 30 minutes and washed with AK-225 (trade name, manufacturedby Asahi Glass Company, Limited) which is a fluorinated solvent, toobtain a substrate having a surface-treated layer.

(Evaluation Methods)

<Method for Measuring Water Contact Angle and n-Hexadecane ContactAngle>

The contact angle of about 2 μL of distilled water or n-hexadecaneplaced on the surface-treated surface of the substrate having asurface-treated layer was measured by a contact angle measuringapparatus DM-500 (manufactured by Kyowa Interface Science Co., Ltd.).Measurement was carried out on different five positions on thesurface-treated surface of the substrate, and their average value wascalculated. To calculate the contact angle, 20 method was employed.

<Initial Water and n-Hexadecane Contact Angles>

With respect to the substrate surface-treated by each of the dry coatingmethod and the wet coating method (the substrate having asurface-treated layer), the initial water contact angle and the initialn-hexadecane contact angle were measured by the above measurementmethod.

<Abrasion Resistance>

With respect to the substrate having a surface-treated layer produced ineach of Ex. 11 to 13, in accordance with JIS L0849, by means of areciprocal traverse tester (manufactured by KNT), a cellulose nonwovenfabric (BEMCOT M-3, manufactured by Asahi Kasei Corporation) wasreciprocated 100,000 times under a load of 1 kg, whereupon the watercontact angle and the n-hexadecane contact angle were measured.

The smaller the decrease of the water repellency (water contact angle)and the oil repellency (n-hexadecane contact angle) when the number ofabrasion times was increased, the smaller the decrease in theperformance by abrasion, and the better the abrasion resistance.

<Fingerprint Stain Removability>

An artificial fingerprint liquid (a liquid composed of oleic acid andsqualene) was deposited on a flat surface of a silicon rubber stopper,and then, excess oil was wiped off with a nonwoven fabric (BEMCOT M-3,manufactured by Asahi Kasei Corporation) to prepare a fingerprint stamp.On a substrate having a surface-treated layer in each of Ex. 11 to 13,the fingerprint stamp was placed and pressed under a load of 1 kg for 10seconds. At that time, the haze at the portion where the fingerprint wasstamped, was measured by a haze meter (manufactured by Toyo Seiki Co.,Ltd.). The value at that time was taken as the initial value. Then, atthe portion where the fingerprint was stamped, by means of a reciprocaltraverse tester (manufactured by KNT) having tissue paper attached,wiping was carried out under a load of 500 g. The haze value wasmeasured after every wiping reciprocation, and if it reached a numericalvalue where the haze is no longer visually observed, within 10 wipingreciprocations, such a case was taken as “acceptable”.

TABLE 1 Fluorinated ether compound Number average OxyperfluoroalkyleneOxyperfluoroalkylene molecular Ex. No. No. unit in block (α) unit inblock (β) Group A Group B weight Ex. 1 Composition (A) 1-3a-1 (CF₂CF₂O)(CF₂CF₂O), CF₃— Formula (2-3) 4,700 (CF₂CF₂CF₂CF₂O) Ex. 2 Compound (B) —(CF₂O), (CF₂CF₂O) — Ex. 3 Composition (C) 1-3b-1 (CF₂O), (CF₂CF₂O)(CF₂CF₂O), CF₃(CF₂)₂— Formula (2-3) 4,700 (CF₂CF₂CF₂CF₂O)

TABLE 2 Dry coating method Wet coating method Fluorinated Water contactn-hexadecane contact Water contact n-hexadecane contact ether angle(degrees) angle (degrees) angle (degrees) angle (degrees) compound After100,000 After 100,000 Fingerprint After 100,000 After 100,000Fingerprint or abrasion abrasion stain abrasion abrasion stain Ex. No.composition Initial times Initial times removability Initial timesInitial times removability Ex. 11 (A) 114.8 112.0 68.9 68.0 Acceptable112.8 111.5 72.9 67.5 Acceptable Ex. 12 (B) 110.8 102.0 66.6 60.9Acceptable 111.3 112.9 66.2 66.6 Acceptable Ex. 13 (C) 117.3 118.0 68.967.3 Acceptable 115.3 116.3 68.5 68.6 Acceptable

As the results in Table 2 show, the substrate having a surface-treatedlayer in each of Ex. 11 and 13, wherein the present compound was used,was excellent in the initial water contact angle and n-hexadecanecontact angle, and particularly in the case of the substrate having asurface-treated layer formed by the dry coating method, the decrease inthe contact angle was small even when abraded 100,000 times. It has beenconfirmed that the present compound having a poly(oxyperfluoroalkylene)chain comprising blocks (α) and (β) is capable of imparting good initialwater/oil repellency to the surface of a substrate and at the same time,has good fingerprint stain removability, is excellent in abrasionresistance whereby the water/oil repellency is less likely to be loweredeven by repeated abrasion, and can be efficiently produced.

The substrate having a surface-treated layer in Ex. 12 wherein afluorinated ether compound having a poly(oxyperfluoroalkylene) chaincomprising (CF₂O) units and (CF₂CF₂O) units was used, was slightly poorin the initial water contact angle and n-hexadecane contact angle, andin the case of the substrate having a surface-treated layer formed bythe dry coating method, the decrease in the contact angle by abrasionwas large.

INDUSTRIAL APPLICABILITY

The fluorinated ether compound of the present invention is useful forsurface treatment to impart water/oil repellency to the surface of asubstrate such as a member constituting a surface to be touched with afinger, of a touch panel.

This application is a continuation of PCT Application No.PCT/JP2013/052944, filed on Feb. 7, 2013, which is based upon and claimsthe benefit of priority from Japanese Patent Application No. 2012-032785filed on Feb. 17, 2012. The contents of those applications areincorporated herein by reference in their entireties.

What is claimed is:
 1. A fluorinated ether compound which has apoly(oxyperfluoroalkylene) chain (αβ) having a structure of block(α)-block (β) or a structure of block (β)-block (α)-block (β), formed bylinking a block (α) comprising at least three C₁₋₃ oxyperfluoroalkyleneunits of at least one type and a block (β) having C₄₋₁₅oxyperfluoroalkylene units of at least one type, wherein the proportionof the C₄₋₁₅ oxyperfluoroalkylene units is at least 30 mol % among alloxyperfluoroalkylene units constituting the block (β), and which has ahydrolysable silyl group on at least one terminal of thepoly(oxyperfluoroalkylene) chain (αβ) via a linking group.
 2. Thefluorinated ether compound according to claim 1, wherein a C₁₋₆perfluoroalkyl group or a C₂₋₆ perfluoroalkyl group having an ethericoxygen atom is bonded via an oxygen atom to the carbon atom at one endof the poly(oxyperfluoroalkylene) chain (αβ), and the hydrolysable silylgroup is bonded via the linking group to the oxygen atom at the otherend of the poly(oxyperfluoroalkylene) chain (αβ).
 3. The fluorinatedether compound according to claim 2, wherein thepoly(oxyperfluoroalkylene) chain (αβ) is a poly(oxyperfluoroalkylene)chain having a structure of block (α)-block (β), and the hydrolysablesilyl group is bonded via the linking group to the oxygen atom of theblock (β).
 4. The fluorinated ether compound according to claim 1,wherein the hydrolysable silyl group is bonded via the linking group toeach end of the poly(oxyperfluoroalkylene) chain (αβ).
 5. Thefluorinated ether compound according to claim 1, which has a numberaverage molecular weight of from 2,000 to 10,000.
 6. The fluorinatedether compound according to claim 1, wherein the block (β) has(CF₂CF₂CF₂CF₂O) units.
 7. A fluorinated ether composition containing atleast 95 mass % of the fluorinated ether compound as defined in claim 1.8. A coating liquid comprising the fluorinated ether compound as definedin claim 1, and a medium.
 9. The coating liquid according to claim 8,wherein the medium contains at least one organic solvent selected fromthe group consisting of a fluorinated alkane, a fluorinated aromaticcompound and a fluoroalkyl ether.
 10. A method for producing a substratehaving a surface-treated layer, which comprises a step of applying thefluorinated ether compound as defined in claim 1 or a fluorinated ethercomposition containing at least 95 mass % of the fluorinated ethercompound to the surface of a substrate by vacuum deposition.
 11. Amethod for producing a substrate having a surface-treated layer, whichcomprises a step of applying the coating liquid as defined in claim 8 tothe surface of a substrate, followed by dying.
 12. The method forproducing a substrate having a surface-treated layer according to claim11, wherein the method of applying the coating liquid to the surface ofthe substrate is a spin coating method, a wipe coating method, a spraycoating method, a squeegee coating method, a dip coating method, a diecoating method, an ink jet method, a flow coating method, a roll coatingmethod, a casting method, a Langmuir-Blodgett method or a gravurecoating method.
 13. The method for producing a substrate having asurface-treated layer according to claim 10, wherein the material forthe substrate is a metal, a resin, glass, a ceramic or a compositematerial thereof.
 14. The method for producing a substrate having asurface-treated layer according to claim 11, wherein the material forthe substrate is a metal, a resin, glass, a ceramic or a compositematerial thereof.
 15. A substrate having a surface-treated layer,obtained by treatment with the fluorinated ether composition as definedin claim
 7. 16. A touch panel having, on its input screen, the substratehaving a surface-treated layer, obtained by treatment with thefluorinated ether composition as defined in claim 7.